Opacifying clusters for use in paint compositions

ABSTRACT

An opacifying cluster which may be added to a coating composition to provide a coating composition with low gloss and a high level of opacity. The opacifying cluster can include a polymeric latex binder coalescing cluster components into a generally homogeneous particle. The cluster components may include discrete polymeric particles each defining a closed void volume therein, a plurality of inorganic pigment particles, and a plurality of extender pigment particles. The clusters may also include a porosity of the polymeric latex binder thereof defining a binder void volume. Also provided is a paint product including such a pigment cluster.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/308,910 filed Mar. 16, 2016, which is hereby incorporated byreference in its entirety.

BACKGROUND

1. Field

This disclosure relates generally to pigment clusters made from abinder, opaque polymer, pigment, and small-size extender. The pigmentclusters may be used in a paint product or paint composition in place ofat least a portion of large-size extender particles to improve theopacity of resultant films made using the paint product whilemaintaining the mechanical integrity and flatness of the resultant filmrelative to a film formed from a paint product that lacks the pigmentclusters.

2. Description of Related Art

Professional and residential consumers of surface coatings, such asarchitectural paints, prefer paint products that require the fewestnumber of applications of paint to cover the surface underneath thepaint being applied.

Certain architectural paints are required by the professional orresidential customer to have a low gloss or flat finish. To achieve suchlow gloss or flat finishes, manufacturers often add large particle sizeextenders which may be ground up minerals (such as calcium carbonate)with an average particle size from about 5 μm to about 50 μm. Such largesize extenders are preferred by manufacturers due to their relativelylow cost and high efficacy at increasing the pigment volumeconcentration of a coating. However, when added to a paint product, thelarge size extenders cause TiO₂, which is nearly universally used inpaint as a white opacifying pigment, or other pigment to crowd and suchcrowding decreases the efficiency of light scattering within the paintwhen it is applied as a surface coating. The large size extenders mayalso cause a reduction in opacity themselves by creating regions of lowlight scattering within the paint when it is applied as a surfacecoating. The consequence of having regions of low light scattering in apaint film is the appearance of microscopic inhomogenieties in the paintfilm. In other words, a coated surface will appear to have “spots” or“windows” on it.

To reduce the negative perception of the appearance of transparentwindows that occur in matte paints which are caused by the presence ofthese large size extenders, manufacturers may increase the amount ofTiO₂ in the paint composition. However, this is not a preferred solutionin part because of the high cost of TiO₂.

The use of clay particles which may have high refraction index oxides orTiO₂ mechanically attached to them is also commonly used in paintproducts as alternative large-size extenders. For example, in U.S. Pat.No. 3,726,700 to Wildt, the use of a composite pigment with clayparticles having TiO₂ and other materials adhered to the clay particlesas a pigment that has high hiding power when used in a paint isdescribed. U.S. Pat. No. 5,551,975 to Freeman et al. describes pigmentsfor paints which are the result of the reaction of clay with colloidalsilica. While such clay-based pigments are important advancements asalternatives to large size extenders for the use in surface coatings,such clay-based pigments do not effectively increase the opacity of apaint film because clay-based pigments tend to uptake the othermaterials within the paint (e.g., solvent, latex, etc.) due to the largesized pores and high porosity of the surface of the clay and, as such,the composite particles tend to lose their void volume, which is a keyrequirement for increasing opacity in a paint film.

The use of vesiculated beads to increase the light scattering (oropacity) of a paint is described in U.S. Pat. No. 4,489,174 toKarickhoff. Such vesiculated beads may increase opacity by up to 15% atlike TiO₂ concentrations when compared to a paint that has beentraditionally formulated with only large size extenders. Suchvesiculated beads are a continuous polymeric matrix that help improvethe opacity and sheen qualities of a surface coating. The limitations ofsuch vesiculated beads are that the beads tend to be costly due in partto the high concentration of polymer in the bead and are difficult tosynthesize with uniformity which causes inconsistent light scatteringefficiency and tint strength.

The use of larger pigment particles with a polymer that is covalentlybonded to the pigment is described in U.S. Pat. No. 7,081,488 to Bardmanet al. These polymer pigment particles purport to improve lightscattering qualities of a paint coating. However, there is not any voidspace in such pigment particles and the cost of such pigment particlesis relatively high.

BRIEF SUMMARY

According to one aspect, an opacifying cluster particle is provided thatis suitable for latex paint compositions to provide increased opacity.The opacifying cluster particle includes a polymeric latex bindercoalescing cluster components into a generally homogeneous particle. Thecluster components include discrete polymeric particles each defining aclosed void volume therein, a plurality of optional inorganic pigmentparticles, and a plurality of optional extender pigment particles. Thepolymeric latex binder further includes a porosity thereof defining abinder void volume of the cluster.

In yet other aspects, the opacifying cluster particle of the precedingparagraph may be combined with one or more optional features. Forinstance, the opacifying cluster particle may have a total void volumeincluding a total closed void volume of all the discrete polymericparticle closed void volumes and the binder void volume of the polymericlatex binder; the total void volume may be from about 1 percent to about35 percent by volume of the opacifying cluster particle; an averageclosed void volume of each discrete polymeric particle may be about 0.4microns to about 0.7 microns in size; an average particle size of theopacifying cluster particle may be from about 5 microns to about 44microns; the opacifying cluster particle may have an outer surfacedefined at least by a portion of the polymeric latex binder and whereinthe outer surface has a surface porosity; the surface porosity may beformed by one or more interstices each from about 0.050 μm to about0.150 μm in size; a glass transition temperature of the discretepolymeric particles may be greater than a glass transition temperatureof the polymeric latex binder; the opacifying cluster may furtherinclude from about 1 percent to about 30 percent by volume of thepolymeric latex binder, from about 10 percent to about 70 percent byvolume of the discrete polymeric particles, from about 0 percent toabout 6 percent by volume of the inorganic pigment particles; and thebalance being the optional extender pigment particles; the pigmentvolume concentration in the opacifying cluster particle may be greaterthan or equal to the critical pigment volume concentration; the extenderpigment particles may be about 0.1 to about 1 microns in size andselected from calcium carbonate, clay, silica, talc, and mixturesthereof; and/or the inorganic pigment particles may be about 0.1 toabout 1.0 microns in size and selected from titanium dioxide, zincoxide, and mixtures thereof.

In yet another aspect, a latex paint composition is described. In someaspects, the latex paint composition includes solvent (such as water),at least one first or primary polymeric binder, pigment particles, and aplurality of discrete opacifying cluster particles. Each discreteopacifying cluster particle may include a second polymeric latex bindercoalescing cluster components into a generally homogeneous particlewherein the second polymeric latex binder is the same as or differentfrom the at least one first polymeric binder. The cluster componentsinclude discrete polymeric particles each defining a closed void volumetherein, a plurality of optional inorganic pigment particles, and aplurality of optional extender pigment particles. The polymeric latexbinder in the cluster has a porosity thereof defining a binder voidvolume.

In other aspects, the latex paint composition of the preceding paragraphmay also be combined with one or motion optional features. For instance,a pigment volume concentration of the discrete opacifying clusterparticles in the latex paint composition may be below the criticalpigment volume concentration; each opacifying cluster particle mayinclude a total void volume including a total closed void volume of allthe discrete polymeric particles closed void volumes and the binder voidvolume of the second polymeric latex binder; the total void volume maybe from about 1% to about 35% by volume of the opacifying cluster, anaverage closed void volume of each discrete polymeric particle may beabout 0.4 microns to about 0.7 microns in size; the pigment particlesmay include one of inorganic pigment particles, the latex paintcomposition may include additional discrete polymeric particles eachdefining a closed void volume therein not coalesced within theopacifying cluster particles, extender pigment particles not coalescedwithin the opacifying cluster particles, and mixtures thereof; the latexpaint composition, when dried, may include about 50 to about 85 volumepercent of the first or primary polymeric binder (15-50 PVC), about 0 toabout 45 percent extender pigment particles not coalesced within theopacifying clusters particles, about 0 to about 20 volume percentdiscrete polymeric particles each defining a closed void volume thereinnot coalesced within the opacifying cluster particles, about 0 to about20 volume percent inorganic pigment particles (such as titaniumdioxide), and about 5 to about 50 volume percent opacifying clusterparticles; the opacifying cluster particles may have an outer surfacedefined at least by a portion of the second polymeric latex binder andwherein the outer surface has a surface porosity; the surface porositymay be formed by interstices each averaging in size from about 0.050microns to about 0.150 microns; a glass transition temperature of thediscrete polymeric particles in the opacifying cluster particles may begreater than a glass transition temperature of the second polymericlatex binder in the opacifying cluster particles; each discreteopacifying cluster particle has an average particle size from about 5microns to about 44 microns; each discrete opacifying cluster particleincludes from about 1% to about 30% by volume of the second polymericlatex binder, from about 10 to about 70 percent by volume of thediscrete polymeric particles, from about 0 to about 6 percent by volumeof the inorganic pigment particles; and the balance being the extenderpigment particles; and/or the pigment volume concentration in thediscrete opacifying cluster particle may be greater than or equal to acritical pigment volume concentration.

In yet another aspect, a latex paint composition exhibiting improvedcontrast ratio and opacity is described herein. In some aspects, thelatex paint composition includes at least solvent, a polymeric latexbinder, optional pigment particles and a plurality of spray driedopacifying cluster particles. Each spray dried opacifying clusterparticle includes discrete polymeric particles each defining a closedvoid volume therein coalesced into a generally homogeneous particle,optional polymeric binder, optional inorganic pigment particles, andoptional pigment extender particles. The latex paint composition, whendried as a paint film, exhibits about 10 to about 35 percentage increasein opacity as compared to a latex paint composition with the same levelof the pigment particles but not including the spray dried opacifyingcluster particles.

In yet further aspects of the latex paint composition, the latex paintof the preceding paragraph may be combined with one or more furtherfeatures. For instance, the latex paint composition may further exhibitabout a one to about a two unit increase (on a 100 basis) or a 0.01 to a0.02 unit increase (on a 1.0 basis) in contrast ratio as compared to alatex paint composition with the same level of the pigment particles butnot including the spray dried opacifying cluster particles; theimprovement in opacity may be exhibited over flat (matte), satins, andeg-shel latex paint compositions with a gloss value from about 0 toabout 30 and a sheen value from about 0 to about 30; a dried latex paintcomposition may exhibit less than about 20 percent increase in gloss andless than about 50 percent increase in sheen upon 25 scrub cycles perthe procedures of ASTM D6736-08; the latex paint composition may includeless than about 10 weight percent of poly vinyl chloride particles (inother approaches, less than 5 percent, in other approaches, less than 1percent, and in yet other approaches, no poly vinyl chloride particles);the latex paint composition may further exhibit an opacity factor ofabout 1:60 to about 1:90 in terms of a ratio of opacity to dry pigment(TiO₂) loading for a matte finish paint; the spray dried opacifyingcluster particle may have a total void volume including a total closedvoid volume of all the discrete polymeric particle closed void volumesand the binder void volume of the polymeric latex binder; the total voidvolume may be from about 1 percent to about 35 percent by volume of thespray dried opacifying cluster particle; an average closed void volumeof each discrete polymeric particle may be about 0.4 microns to about0.7 microns in size; an average particle size of the spray driedopacifying cluster particle may be from about 5 microns to about 44microns; the spray dried opacifying cluster particle may have an outersurface defined at least by a portion of the polymeric latex binder andwherein the outer surface has a surface porosity; the surface porositymay be formed by one or more interstices each from about 0.050 μm toabout 0.150 μm in size; a glass transition temperature of the discretepolymeric particles may be greater than a glass transition temperatureof the polymeric latex binder; the latex paint composition may furtherinclude from about 1 percent to about 30 percent by volume of thepolymeric latex binder, from about 10 percent to about 70 percent byvolume of the discrete polymeric particles, from about 0 percent toabout 6 percent by volume of the inorganic pigment particles; and thebalance being the pigment extender particles; the pigment volumeconcentration in the spray dried opacifying cluster is greater than orequal to the critical pigment volume concentration; the optionalextender pigment particles are about 0.1 to about 1 microns in size andselected from calcium carbonite, clay silica, talc, and combinationsthereof; and/or the latex paint composition may further include anopacity factor of about 1:60 to about 1:90 in terms of a ratio ofopacity to dry pigment (TiO₂) loading.

In yet further aspects, a latex paint composition exhibiting improvedcontrast ratio and opacity over a wide range of gloss values and, insome instances, a wide range of pigment volume concentrations. In someapproaches, the latex paint composition includes solvent, a polymericlatex binder, and pigment particles wherein the latex paint composition,when dried as a paint film, exhibits about 10 to about 35 percentageincrease in opacity as compared to a latex paint composition with thesame level of the pigment particles but not including the spray driedopacifying cluster particles; and wherein the improvement in opacity isexhibited over flat (matte), satins, and eg-shel latex paintcompositions with a gloss value from about 0 to about 30 and a sheenvalue from about 0 to about 30. The latex paint composition may alsoinclude a plurality of spray dried opacifying cluster particles, whereineach spray dried opacifying cluster particle may include discretepolymeric particles each defining a closed void volume therein andcoalesced into a generally homogeneous particle, optional polymericbinder, optional inorganic pigment particles, and optional pigmentextender particles.

In yet other aspects, an additive for use in a coating composition isdescribed herein where the additive includes a first component having afirst refractive index, and a second component having a secondrefractive index. The first component and the second component areconnected by a coalesced latex binder material.

The additive of the preceding paragraph may be combined with any of theoptional features described in any of the above paragraphs and, forexample, may further define the first refractive index from about 1 toabout 1.5 and the second refractive index from about 1.5 to about 3.0;and/or wherein the difference in refractive indices between the firstcomponent and the second component is at least about 0.5 to about 2.0

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWING

The disclosure may take physical form in certain parts and arrangementof parts, embodiments of which will be described in detail in thisspecification and illustrated in the accompanying drawings which form apart hereof and wherein:

FIG. 1 shows a top view of: region (a), which is an exemplary embodimentof a surface coated by a paint having only large-size extenders, andregion (b), which is an exemplary embodiment of a surface coated by apaint including opacifying clusters in place of at least a portion ofthe large-size extenders included in the paint shown in region (a);

FIG. 2(a) shows a schematic, cross-sectional view of an exemplaryembodiment of an opacifying cluster;

FIG. 2(b) shows a schematic, cross-sectional view of an alternativeexemplary embodiment of an opacifying cluster;

FIG. 3 shows a schematic view of equipment that may be used to produceopacifying clusters;

FIG. 4 shows a schematic, cross-sectional view of an alternativeexemplary embodiment of an opacifying cluster;

FIG. 5 shows a graphical representation of the size distribution ofopacifying clusters compared to a large-size extender;

FIG. 6(a) shows a graphical representation of the opacity of thesurfaces coated by paints having large-size extenders versus paintsopacifying clusters;

FIG. 6(b) shows a graphical representation of the sheen ofrepresentative surfaces coated by paints having large-size extendersversus paints having opacifying clusters; and

FIG. 7 shows a graphical representation of the ability of clusters toprovide opacity similar to prior opaque polymers and relative to theinability of large size extenders to improve opacity; and

FIG. 8 shows a graphical representation of the ability of opacifyingclusters herein to reduce sheen similar to other large particle sizeextenders and as compared to prior opaque polymers inability to achievesuch results.

The drawings herein are not necessarily drawn to scale and schematicviews do not necessarily represent the actual product or componentsthereof, but intended to generally represent various components thereof.

DETAILED DESCRIPTION

Certain terminology is used herein for convenience only and is not to betaken as a limitation on the present disclosure. Relative language usedherein is best understood with reference to the drawings, in which likenumerals are used to identify like or similar items. Further, in thedrawings, certain features may be shown in somewhat schematic form.

It is also to be noted that the phrase “at least one of”, if usedherein, followed by a plurality of members herein means one of themembers, or a combination of more than one of the members. For example,the phrase “at least one of a first widget and a second widget” means inthe present application: the first widget, the second widget, or thefirst widget and the second widget. Likewise, “at least one of a firstwidget, a second widget and a third widget” means in the presentapplication: the first widget, the second widget, the third widget, thefirst widget and the second widget, the first widget and the thirdwidget, the second widget and the third widget, or the first widget andthe second widget and the third widget.

Glossary of Terms

“Opacity” as used herein refers to the ability of a film to scatterlight based on the thickness of the film. The opacity is often expressedas S/mil and may be in the form of Kubelka-Munk scattering coefficientsas determined using a modification of ASTM D2805-70 as described by J.E. McNult and H. L. Ramsey in American Paint and Coatings Journal, April1988 p. 46 by the weight drawdown method, which is incorporated hereinby reference.

“Opaque polymer” as used herein refers to a polymer or polymeric networkthat encloses or substantially encloses a defined volume. An opaquepolymer may be a discrete polymeric particle where each polymer particledefines a closed void volume therein. In some embodiments, an opaquepolymer comprises polystyrene. Opaque polymers are commerciallyavailable from commercial vendors. Exemplary commercially availableopaque polymers are Ropaque Ultra EF and/or Ropaque OP-96 EF (bothavailable from the Dow Chemical Company, Midland, Mich.). In certainembodiments the defined volume of an opaque polymer comprises airforming a void that scatters light. In certain other embodiments thedefined volume of an opaque polymer comprises a liquid such as water.For embodiments including a liquid within the defined volume, the liquidis eventually replaced with air, creating a void that scatters light.Opaque polymers may be used as a partial replacement for TiO₂ in paintsor other coatings to enhance hiding and whiteness in paints andcoatings.

“Binder void volume” as used herein refers to the volume percentage of acoalesced polymer structure (such as a coalesced binder) that comprisesair when applied as a part of a coating to a surface and dried.

“Opaque polymer void volume” as used herein refers to the volume of thevoid that is enclosed by, or substantially enclosed by, an opaquepolymer.

“Void volume” or total void volume as used herein refers to the volumepercentage of a material that comprises air when applied as part of acoating to a surface and dried. Void volume or total void volume isgenerally the sum of opaque polymer void volume and binder void volume.

“Pigment clusters” or opacifying cluster as used herein generally refersto different components, such as binder, opaque polymer, pigment,extenders, and/or other materials which may be used to enhance, orotherwise change the properties of, a paint composition wherein thecomponents may be coalesced together into particles as are describedherein. In some embodiments, pigment clusters and opacifying clustersare not held together with chemical bonding or covalent bonding. Inother embodiments, components of pigment clusters and opacifyingclusters (such as pigment) are not held to other components (such asbinder) with hydrogen bonding or other types of bonding.

“Pigment volume concentration” or “PVC” as used herein refers to anumber that represents the volume of pigment compared to the volume ofall solids. In the field of paints and coatings, PVC is a useful measurebecause the binder acts as the material to unite all the pigment andother raw materials into the paint and the PVC value ensures there isenough binder to enable the paint to adhere properly to whatever it hasbeen applied over in addition to containing all of the other componentsof the paint. If a paint has no pigment at all it will usually be veryglossy and have a PVC of zero. An example is clear gloss paints. Flatpaints have a very high pigment loading and have high PVCs (usually inthe range from about 55% up to about 80%). Another non-limitingexemplary range of PVC in which pigment can be loaded is from about 60%to about 75%. Primers and undercoats vary from 30% to about 50% PVC asdo semi-gloss, satin and low sheen paints. Gloss colored paints can varyfrom 3% to about 20% PVC depending on the color of the paint. Generallythe darker the color of the gloss paint the lower the PVC. Additionally,it is thought that the lower the PVC of a paint is, the better itsmechanical properties (such as tensile strength, and consequently,exterior durability) will be. PVC may be expressed as a percentage. Forexample, if a coating has a PVC of 30, then 30% of the totalbinder/pigment blend is pigment, and 70% is binder solids on a volumebasis.

“Critical pigment volume concentration” or “CPVC” as used herein is thepoint at which there is just enough binder to wet (entirely surround)the pigment particles. As PVC reaches and then increases above CPVC,mechanical properties of the paint deteriorate. Above CPVC, withinsufficient binder to satisfy pigment surface and fill interstitialspaces, air is introduced into the film resulting in a decrease in filmintegrity. However, above CPVC, increased air and pigment interfaceresults in a substantial boost in pigment scattering efficiency. A filmbelow the CPVC has excess resin and may exhibit a smooth surface thatreflects light or appears to be glossy. As the PVC of a film approachesCPVC, the film will appear to be flatter, although the aforementionedloss of mechanical properties may become a limiting factor in how closeto CPVC a paint producer wishes to provide the PVC.

“Y_(black)” as used herein represents the reflectance value of a coatingand measures the ability of a coating to cover against a blackbackground. Measurement of Y_(black) may be done as part of measurementof contrast ratio.

“Y_(white)” as used herein represents the reflectance value of a coatingand measures the ability of a coating to reflect light against a whitebackground. Measurement of Y_(white) may be done as part of measurementof contrast ratio.

“Contrast Ratio” as used herein is calculated as Y_(black)/Y_(white) andis the ratio of the reflectance of a film on a black substrate to thatof an identical film on a white substrate. ASTM D2805-11 provides forthe measurement of contrast ratio.

“Binder” as used herein is a material that may be used to form a clusterfrom different components (ex., pigments, small sized extenders, and/oropaque polymers) by coalescing and mechanically connecting thecomponents. Latex polymers are a non-limiting example of a binder thatmay be dispersed in water using a dispersant and film formation (orother network formation) occurs by joining (or coalescence) of thesesolid particles as water evaporates or is otherwise driven off.Exemplary binders which may be used in the present disclosure include,but are not limited to, polyvinyl acetates, vinyl acrylics, styrenebutadiene, styrene acrylics, and ethylene vinyl acrylics. Otherexemplary binders include, but are not limited to solvent-borne bindersand water reducible binders.

“Small size extender” as used herein refers to particles of minerals,clay, ground and precipitated silica, or other fillers which may be usedto reduce the quantity of the pigment required to achieve a desiredhiding ability, sheen, etc., without significantly affecting the colorof the paint established by the pigment, and having a particle size offrom about 0.1 μm to about 1 μm. Small size extenders that may bepurchased commercially include, but are not limited to Omyacarb UF (OmyaNorth America). Extender pigment particles used within a cluster may besmall size extender particles. Any suitable small size extender that oneof skill in the art would use in a coatings application may be used inthe coatings and paint products of the present disclosure withoutdeparting from the scope of the present disclosure.

“Large size extender” as used herein refers to particles of minerals,clay, or other fillers which may be used to reduce the quantity of thepigment required to achieve a desired hiding ability, sheen, etc.,without significantly affecting the color of the paint established bythe pigment, and having a particle size of greater than 5 μm. In someembodiments a large size extender is from about 5 μm to about 50 μm. Inother embodiments, a large size extender is from about 10 μm to about 15μm. Extender pigment particles not used or coalesced within anopacifying cluster, but otherwise added to a latex paint composition maybe large size extender particles.

“Pore” or interstices as used herein is an opening at the surface of astructure such as a polymer, polymer cluster, or opacifying cluster. Inone embodiment, a pore may form at the outer surface of an opacifyingcluster and the components of the outer surface of an opacifying clustermay comprise components selected from the group consisting of: binders,opaque polymers, small-size extenders, pigments, and combinationsthereof.

“Sheen” as used herein may also sometimes be referred to as “gloss”. Itis thought that because most extenders have a refractive index of lightthat is close to the refractive index of the binders of most coatings,below CPVC an extender/latex film will be largely transparent to visiblelight. In a coating, a gloss finish indicates that the surface which hasa coating applied to it (i.e., is “finished”) it is shiny or glass-like.The gloss of a surface is described as the reflection of light from thesurface that is independent of color. ASTM D523 or D532-14 may be usedto measure sheen. The prescribed angle at which light is reflected offthe surface may vary, but for the purposes of this disclosure to measure85 Sheen, is measured at 85° relative to the surface reflecting thelight. ASTM D523 or D532-14 may also be used to describe 60 Gloss whichis measured at 60° relative to the surface reflecting the light. One ofskill in the art is able to determine relative levels of gloss (lowversus high) in context of each coating.

“Paint” as used herein refers to any mixture comprising different typesof raw materials, each with its own function, which must be balanced toachieve the desired properties in the final product or film coating. Thetwo primary functions of paint are decoration and protection. A paintmay contain a solvent (which can include a volatile component derivedfrom a petroleum distillate for a solvent-based paint, or a low VOC, orno-VOC, or water for a water-based paint), a binder, a pigment, fillers(such as an extender or a plurality of extenders of different sizes) andan additive, which may impart different functionality to the paint orfinal coating. Embodiments may include an opacifying cluster as acomponent thereof, optionally in combination with at least one of thesolvent, binder, pigment, filler and additive.

“Burnish” as used herein refers to the ability of a coating to retainits gloss value after being subjected to mechanical forces, such asabrasion. Burnish may be measured through ASTM D6736-08.

“Refractive Index” as used herein refers to a measurement that describeshow light propagates through a material or medium. If needed, RefractiveIndex may be measured through one or more of ASTM D1218, D1747, or D542.

Opacifying Cluster Particle Constituents

The present disclosure is directed to compositions of, methods forusing, and methods for making opacifying cluster particles that arecompatible to form a component of surface coatings such as latex paintswhich provide, among other features, a surface film of low gloss andhigh opacity. The unique opacifying clusters of the present disclosureincrease opacity with increasing PVC similar to the commonly used prioropaque polymers, but contrary to the prior opaque polymers, theopacifying clusters herein can also be used to reduce gloss and sheen(similar to large size extender particles) to achieve a matte oregg-shell finish. Thus, the clusters herein may be used over a widerange of gloss and sheen values not previously obtainable withconventional opaque polymers.

Turning to more of the specifics, FIG. 1 shows an exemplary top view ofan applied film 10 of paint against a white backing 11 in region (a),which is shown extending beyond the lowermost boundary of the film 10 inFIG. 1 for illustrative purposes, wherein the applied film containslarge size extenders and there is the appearance of windows 12 (shown aslight spots in FIG. 1 relative to the surrounding film material) in theapplied film 10. The formation of such windows is undesirable to usersbecause of the need for additional coatings of paint to completely hidea substrate. Region (b) in FIG. 1 includes an applied film 10 against awhite backing 11 similar to that in region (a), wherein the applied film10 in region (b) is formed with a paint including the opacifyingclusters disclosed herein. In the surface coating which is preparedincluding the opacifying clusters there is a greatly reduced appearanceof windows 12 in the applied film 10, however, the complete absence ofwindows 12 is not required. In some embodiments the binder polymer iscoalesced to form a network or backbone. In other embodiments the binderpolymer is not covalently bonded to the other constituents. In certainembodiments the opaque polymer particles are discrete polymericparticles. In certain other embodiments the opaque polymer is processedwith the outlet temperature being high enough (for example, above theglass transition temperature (T_(g)) of the opaque polymer), asdescribed in detail below with respect to the Manufacture of Opacifyingclusters. In yet other embodiments still, the opaque polymer iscoalesced to other opaque polymer or binder.

FIG. 2(a) shows the cross sectional view of an exemplary embodiment ofan opacifying cluster 20. The cluster 20 comprises a volume of bindermaterial 23 having an outer surface 21 wherein the outer surface furthercomprises a plurality of interstices or pores 22. The plurality of pores22 collectively establish the porosity of the opacifying cluster 20. Inone embodiment the outer surface 21 comprises a binder material orpolymeric latex binder. In another embodiment the outer surfacecomprises any number of components which may be selected from the groupconsisting of: binders, opaque polymers, pigments, small-size extendersand combinations thereof. In some embodiments the interstices or pores22 have a diameter or size of from about 0.050 μm to about 0.150 μm. Inother embodiments the pores have a diameter or size of about 0.1 μm.Without wishing to be limited by theory, it is thought that because ofthe relatively small pore diameter or size and the relative tortuosityof the inner structure of an opacifying cluster 20, the latex from thepaint solution does not enter into the voids (both the voids within theopacifying cluster 20 and the voids 28 in any binder) within theopacifying cluster 20 (i.e., the latex material does not displace theair inside the voids inside the opacifying cluster 20), thus preservingthe optical qualities such as the light scattering ability of theopacifying cluster 20, rendering the opacifying cluster 20 an effectivealternative to large-size extenders—unlike clays, for example, which arepenetrated by the latex material from a paint solution, thus causing theclay particles to lose their optical qualities.

The opacifying cluster 20 further comprises binder material or polymericlatex binder 23 which mechanically coalesces or binds the variouscomponents of the opacifying cluster 20 to form a mixture, including anopaque polymer 24, small-size extender 25 (or extender pigmentparticles), and/or pigment 26 (or inorganic pigment particles). Theopaque polymer 24 may comprise polymer which encloses or substantiallyencloses an opaque polymer void volume 27. The opaque polymer 24 mayinclude discrete polymeric particles each defining a closed void volumetherein. In some embodiments the polymer of the opaque polymer ispolystyrene. Suitable opaque polymers may be available from commercialvendors such as Ropaque Ultra EF or Ropaque OP-96 EF (both availablefrom the Dow Chemical Company, Midland, Mich.). In some embodiments theopaque polymer void volume 27 has a diameter or size from about 0.3 μmto about 0.8 μm. In other embodiments the opaque polymer void volume 27has a diameter of from about 0.4 μm to about 0.7 μm. In otherembodiments still the opaque polymer void volume 27 has a diameter offrom about 0.5 μm to about 0.6 μm. In some embodiments the opaquepolymer 24 has a polymer thickness of from about 0.075 μm to about 0.150μm. In other embodiments the opaque polymer has a polymer thickness offrom about 0.100 μm to about 0.120 μm. The opacifying cluster 20 alsocomprises a binder void volume 28 which is the result of empty spaceswhich form within the opacifying cluster 20 during formation of thecluster—for example, during spray drying.

FIG. 2(b) shows an alternative embodiment of an opacifying cluster 20 ofthe present disclosure. In the embodiment shown in FIG. 2(b) the outersurface 21 may comprise binder material 23 and opaque polymer 24,pigment 26, and small-size extender 25. As described in additionaldetail herein, the amount of polymer 24, pigment 26 and small-sizeextender 25 may vary from opacifying cluster to opacifying cluster anddepends on the input feeds during the manufacture of the opacifyingclusters. Surprisingly, it is discovered that not all components arenecessary to provide functional opacifying clusters. For example, FIG. 4shows yet an additional embodiment of an opacifying cluster 20 of thepresent disclosure. In the embodiment of FIG. 4 the opacifying clustercomprises only opaque polymer 24 which has been processed at atemperature that is significantly above T_(g) of the opaque polymer 24.

The binder material or polymeric latex binder 23 may have a relativelylow glass transition temperature (T_(g)) and in some embodiments theT_(g) of the binder material 23 is from about 0° C. to about 60° C. Inother embodiments the T_(g) of the binder material 23 is from about 5°C. to about 60° C. In another embodiment still, the T_(g) of the bindermaterial 23 is from about 15° C. to about 50° C.

The opaque polymer 24 or the polymer of the discrete polymeric particleseach defining a closed void volume therein may have a relatively highglass transition temperature (T_(g)) and in some embodiments the T_(g)of the opaque polymer is from about 100° C. to about 120° C. In otherembodiments the T_(g) of the opaque polymer is from about 100° C. toabout 110° C.

In some embodiments, the difference in T_(g) of the binder 23 to theT_(g) opaque polymer 24 is greater than 80° C. In other embodiments, thedifference in T_(g) of the binder to the T_(g) opaque polymer is greaterthan 40° C. In other embodiments, still the difference in T_(g) of thebinder to the T_(g) opaque polymer is greater than 10° C.

In some embodiments, the binder is a latex material. Exemplary binderswhich may be used in the present disclosure include, but are not limitedto, polyvinyl acetates, vinyl acrylics, styrene butadiene, styrenes,styrene acrylics, ethylene vinyl acrylics. Other exemplary binders aresolvent-borne binders and water reducible binders.

One suitable non-limiting example of a material to use as the pigment orinorganic pigment particle 26 is TiO₂. In other embodiments the pigment26 comprises zinc oxide. It is to be understood, however, that the scopeof the present disclosure is not limited to titanium dioxide or zincoxide as the pigment and that any suitable material may be used. In someembodiments the pigment 26 has a diameter of from about 0.1 μm to about1.0 μm. In other embodiments the pigment 26 has a diameter of from about0.3 μm to about 0.5 μm.

In an embodiment, the small-size extender 25 (or extender pigmentparticles within the cluster) of the present disclosure could be CaCO₃.Other non-limiting examples of materials which may be used as small-sizeextenders are clay, silica (both ground and precipitated), a fine talcor any other small extender that may be used in the art, andcombinations thereof. In some embodiments, the small-size extenders 25are from about 0.1 μm to about 1.0 μm. In other embodiments, the smallsize extenders 25 are from about 0.3 μm to about 0.8 μm. In otherembodiments, still the small size extenders 25 are from about 0.5 μm toabout 0.7 μm. In some embodiments, the opacifying cluster 20 does nothave any small-size extender 25.

The opacifying clusters 20 are formed through mechanical entanglement orcoalescence of the binder and the constituents. In some approaches,there is no covalent or chemical bonding within the clusters. Theformation of the opacifying clusters 20 via temperature elevation (usinga method such as spray drying) provides for relatively uniformopacifying clusters 20. The opacifying clusters 20 also which have voidvolumes that comprise both opaque polymer void volume 27 and binder voidvolume 28 due to the water being driven out of the binder in theopacifying clusters 20. In certain non-limiting embodiments, the voidvolume is from about 1% to about 35% by volume of the opacifying cluster20. In other non-limiting embodiments, the void volume is from about 15%to about 30% by volume of the opacifying cluster. In other non-limitingembodiments still, the void volume is from about 25% to about 30% byvolume of the opacifying cluster.

In some exemplary opacifying clusters 20, the volume percentage ofsolids of pigment 26 in an opacifying cluster 20 is from 0 to about 6%.In other exemplary embodiments, the volume percentage of solids ofpigment 26 in an opacifying cluster 20 is greater than or equal to CPVC.In still other embodiments, the volume percentage of solids of pigment26 in an opacifying cluster is about 1 to about 6%, in other approaches,about 2 to about 4%, and in yet other approaches, about 2.5%.

In other exemplary embodiments, the volume percentage of solids ofbinder in an opacifying cluster 20 is from about 1% to about 30%. Inanother exemplary embodiment, the volume percentage of solids of binderin an opacifying cluster is from about 5% to about 30%.

Some embodiments of the present opacifying cluster 20 have a volumepercentage of solids of opaque polymer 24 of from about 0% to about 90%.In other exemplary embodiments, the volume percentage of solids ofopaque polymer 24 in an opacifying cluster 20 is from about 10% to about70%. In other exemplary embodiments still, the volume percentage ofsolids of opaque polymer 24 in an opacifying cluster 20 is from about30% to about 50%.

In some exemplary embodiments, the volume percentage of solids ofsmall-size extender 25 is from about 0% to about 90%. In manyembodiments the volume percentage of solids of small size extender 25comprises the balance of the opacifying cluster.

In some exemplary approaches, the opacifying clusters may exhibit adensity of about 7 to about 20 pounds/gallon. In other approaches, theopacifying clusters may exhibit a density of about 7 to about 15pounds/gallon, and in yet other approaches, about 10 to about 12 poundsper gallon. It will be appreciated, that such exemplary densities applyto all the various approaches of opacifying clusters provided herein.

In some aspects, the opacifying clusters herein are structured orengineered composite particles including the various particleconstituents or components described throughout this disclosure. Theconstituents or particle components are generally uniformly orhomogeneously dispersed or spread consistently throughout the compositeparticle. In some approaches, the cluster particles are spray driedparticles. In other words, and in some approaches, the compositeparticles of this disclosure are not a core/shell-type structure and arefree-of or devoid of any coatings or surface layers thereof prior tobeing combined in a latex paint composition.

Manufacture of Opacifying Clusters

FIG. 3 provides a spray dryer 30 that may be used to manufacture theopacifying clusters of the present disclosure. According to theembodiment illustrated in FIG. 3, the spray dryer 30 includes an airsupply blower 31 that feeds inlet air into a chamber 36 for atomizing aslurry comprising components to be included in the opacifying clusters20, such as pigment 26, opaque polymer 24, and latex, for example. Theair supply blower 31 can be a rotary, positive displacement fan,turbine, or any other suitable airflow device that can supply thevolumetric flow rates into the chamber 36 to achieve the atomizationdescribed herein. An electric air heater 34 such as a radiant element,steam conduit, or other suitable heat source in thermal communicationwith the air supplied by the air supply blower 31 is operable toestablish the desired temperature of the inlet air being introduced tothe chamber 36 via a nozzle 38. The atomized slurry is drawn from thechamber 36 into a cyclone dryer 33 by a negative pressure established byan exhaust blower 32 which, like the air supply blower 31, can be arotary, positive displacement fan, turbine, or any other suitableairflow device that can establish the exhaust volumetric flow ratesdescribed herein. Once through the chamber 36, the entrained opacifyingclusters 20 in the form of a dry powder are removed from the airflow bya filter 33. The filter 33 can be any suitable separation device thatcan remove a substantial portion of the entrained powder from theairflow such as a cyclone separator, for example, that uses centrifugalforce to expel the entrained produce radially outward, toward aperforated peripheral wall provided with a filter material, for example.The airflow can be occasionally interrupted to allow the particulateopacifying clusters 20 to be deposited into a collection container 37,which can be isolated from the system with a large ball valve 40 orother suitable flow control device.

A controller 39 is provided to control operation of the variouscomponents of the spray dryer 30 in accordance with the methods ofmanufacturing the opacifying clusters 20 described herein. An embodimentof the controller 39 generally includes a non-transitory,computer-readable medium 41 storing computer-executable instructionsthat, when executed by a computer processor 42, cause the controller 39to communicate with the various operational components of the spraydryer 30 to manufacture the opacifying clusters 20 under the conditionsdescribed herein.

In use, the inlet air supply blower 31 and the exhaust blower 32 arestarted by the controller 39 to introduce a suitable amount of nozzleair to assist in atomization of the opacifying cluster slurry. Filters33 on the spray dryer 30 are equipped with an air pulse mechanism 44 tooccasionally release powder from filters 33. The electric air heater 34is then set to deliver the desired temperature at the inlet 35.

When the temperature of the outlet of the chamber 36 reaches about 85°C. then water is pumped to the atomizer at a rate to maintain a constantoutlet temperature. Once the spray dryer 30 has reached steady statewith the desired outlet temperature with only water and atomization air,the water feed is switched to the slurry including the components to beincluded in the opacifying clusters 20. Once through the chamber 36, theresultant dry powder is separated in a cyclone and collected in acontainer 37 using the ball valve 40 or any other valve that may bewell-suited for such an application.

FIG. 4 shows a cross-sectional view of an exemplary opacifying cluster20 of the present disclosure, comprising only opaque polymer 24 whichhas been processed at a very high outlet temperature (above the T_(g) ofthe opaque polymer 24) to coalesce the opaque polymers 24 together. Inthe opacifying cluster 20 shown, the opaque polymer 24 is distributed ina higher amount towards the outer surface 21 of the opacifying cluster20 than within a central region of the opacifying cluster 20. Withoutwishing to be limited by theory, it is thought that during themanufacturing process, as water that acts as a carrier of the componentsinto the spray dryer evaporates during the spray drying process, lighterand/or less dense components (such as opacifying clusters) are movedtowards the outer surface. In other embodiments, binder material mayalso coalesce at the outer surface according to the same proposedprinciple.

Size Distribution of the Opacifying Cluster

An exemplary volume percentage of opacifying clusters 20 included in anillustrative embodiment of a paint composition is from about 50% toabout 60%. In certain embodiments, the volume percentage of opacifyingclusters in a paint composition is less than or equal to CPVC.

FIG. 5 shows the distribution of sizes of the opacifying clusters of thepresent disclosure as well as the distribution of particle sizes inexemplary large-size extenders (Duramite, available from ImerysPerformance Materials, Roswell, Ga.) which are viable for commercialuse. Surprisingly, it is found that the opacifying clusters madeaccording to the present disclosure are substantially similar in size(i.e., have a relatively uniform size distribution) when compared to theexemplary large-size extenders. From FIG. 5 it is clear that theopacifying clusters of the present disclosure are substantially similarin size distribution to comparable commercially available large-sizeextenders. In one embodiment, the opacifying clusters have an averageparticle size of from about 5 μm to about 44 μm. In another embodiment,the opacifying clusters have an average particle size of from about 7 μmto about 30 μm. In another embodiment still, the opacifying clustershave an average particle size of from about 10 μm to about 20 μm. In yetanother embodiment, the opacifying clusters have an average particlesize of from about 10 μm to about 15 μm. It is highly desirable toprovide consistently-sized and relatively small (greater than 325 meshin size) extenders for an even, non-grainy, composition when theopacifying clusters are used in a paint coating.

Properties of the Composition

When added to a paint composition as a replacement for at least aportion, which can optionally be less than all, or optionally all of thelarge size extenders, the opacifying clusters of the present disclosureprovide improved optical properties compared to a control paintcomposition which utilizes large size extenders that is devoid of theopacifying clusters described herein. Table 1 shows the comparison of anexemplary paint composition that includes opacifying clusters and acontrol paint composition that does not contain any opacifying clusters.

From Table 1 we can see that the paint clusters provide an improvementin the contrast ratio (C/R) and opacity (S) of the composition. In Table1: NVV is volume solids, PVC is pigment volume concentration, extenderand TiO₂ levels are expressed as pounds per 100 gallons or if easierdivide by 100 to express as pound/gal. The TiO₂ is actually a 75% slurry(i.e., the actual level of TiO₂ may be calculated by multiplying thelisted amount by 0.75). Y is the reflectance over white and black,respectively, and C/R is the contrast ratio.

TABLE 1 Performance Results of a Paint Composition Having Opacifyingclusters Large-Size Opacifyin TiO₂ Measured 85 Sample Extender g clusterslurry NVV PVC Y_(white) Y_(black) C/R wt/gal S/mil 60 gloss sheenControl 140 0 212 41.7 30.8 0.9079 0.8548 0.942 10.84 1.86 10.8 11.5Sample A 0 75 212 41.7 30.8 0.9229 0.8879 0.962 10.32 2.47 10.6 12.2

The contrast ratio of Sample A is higher than the contrast ratio (C/R)of the Control that does not have the opacifying clusters. The opacity(S/mil) of Sample A is about 32% higher than the opacity of the Control.

FIG. 6(a) is a graphical representation of measurements of opacity ofcoatings applied from paint compositions containing exemplary opacifyingclusters having 42.5 PVC opaque polymer, 42.5 PVC CaCO₃, 5 PVC TiO₂, andthe balance of the opacifying cluster being latex versus an equal amountof ground calcium carbonate (used as a large-size extender). The paintused comprises about 38% binder, 10% water, 13% large size extender, 20%pigment slurry, and the balance being other additives. The x-axis is theextender PVC of the paint. The cluster composition of the graph is apaint with both clusters and large size extenders. From a paintformulation perspective, increasing PVC replaces latex with extender oropacifying clusters. Both the large-size extender and the opacifyingclusters improves the opacity of the resultant coating.

FIG. 6(b) is a graphical representation of sheen measurements of thecompositions described in FIG. 6(a). The composition that contains thelarge-size extender and the opacifying clusters (i.e., clustercomposition) has a sheen that is relatively high whereas the compositionthat contains the opacifying clusters has a relatively low sheen.

An exemplary embodiment of a paint according to the present disclosureis a paint product comprising at least one solvent, at least one binder,at least one pigment and a PVC of opacifying clusters wherein the PVC ofopacifying clusters in the paint is below CPVC. However, embodiments ofthe opacifying clusters comprise a PVC of pigment in the opacifyingclusters that approaches CPVC.

In yet other aspects, the opacifying clusters herein may be structuredor spray dried granular optical particles for use in coatings, such aslatex paint compositions. The clusters may include different opticallyactive components coalesced within the particle and with selectedrefractive indexes so that the opacifying cluster includes one or morediscrete components with refractive indexes from 1 to 3.0. A differenceof refractive index between the first component and the second componentmay be about 0.5 to about 2.0

For instance and in one approach, the opacifying clusters herein mayinclude a first component or particle therein with a first refractiveindex. The first component or particle may have a refractive index ofabout 1.5 to about 3.0, in other approaches, about 1.5 to about 2.7, andin other approaches, about 2.0 to about 3.0. In some approaches, thefirst component may be an inorganic pigment particle such as titaniumdioxide, latex binder, calcium carbonate and the like, and combinationsthereof.

The opacifying cluster may also include a second component or particlewith a second refractive index different than the first refractiveindex. The second component or particle may have a refractive index ofabout 1.0 to 2.0, in other approaches, 1.0 to about 1.5, and in otherapproaches, 1.2 to about 2.0, and in yet other approaches, 1.0 to 1.2.In some approaches, the second component may be a discrete polymerparticles defining an internal void of air or water. In otherapproaches, the second component may be an opaque polymer. The internalvoid of the second component may be 0.3 to about 0.8 microns in size.

In some approaches, the cluster may include yet another or thirdcomponent or particle with a third refractive index that may be the sameas to different than either the first or second refractive index. Thethird component may have a refractive index from about 1.4 to about 2.0.The third component may be a small size extender particle. The first,second, and third components or particles may be coalesced into acomposite particle by a latex binder.

EXAMPLES

The practice and advantages of the opacifying clusters and latex paintcompositions including such clusters may be demonstrated by thefollowing examples, which are presented for purposes of illustration andnot limitation. Unless otherwise indicated, all amounts, percentages,and ratios are by weight.

Example 1

An exemplary opacifying cluster is prepared by spray drying a 50% solidsslurry of Omyacarb UF, OP-96, TiO₂ and Latex. On a volume basis, thefinished cluster comprises 42.5 Omyacarb UF, 42.5% OP-96, 5% TiO₂ and10% latex binder. The average particle size of the Opacifying clustersmeasured using a Malvern Mastersizer (Malvern Instruments, Malvern, UK)is 12 microns.

Example 2

Another exemplary opacifying cluster is prepared by spray drying a 44%solids slurry of hydrite clay, OP-96, TiO₂ and latex. On a volumepercentage of solids basis, the finished cluster comprises 37.5% clay,37.5% OP-96, 5% TiO₂ and 20% latex binder. The average particle size ofthe Opacifying clusters is 12.7 microns.

Example 3

Another exemplary opacifying cluster is prepared by spray drying a 50%solids slurry of Omyacarb UF, OP-96 and latex. On a volume percentage ofsolids basis, the finished cluster comprises 30% Omyacarb UF, 60% OP-96and 10% latex binder. The average particle size of the Opacifyingclusters is 14.6 microns.

Example 4

Another exemplary opacifying cluster is prepared by spray drying a 31%solids slurry of OP-96 and latex. On a volume percentage of solidsbasis, the finished cluster comprises 90% OP-96 and 10% latex binder.The average particle size of the Opacifying clusters is 13.2 microns.

Example 5

Another exemplary opacifying cluster is prepared by spray drying a 60%solids slurry of Omyacarb UF, TiO₂ and latex. On a volume percentage ofsolids basis, the finished cluster is composed of 85% Omyacarb UF, 5%TiO₂ and 10% latex binder. The average particle size of the Opacifyingclusters is 12.7 microns.

Examples 6-17

The properties of opacifying clusters versus a commercially availablelarge-size extender is CaCO₃ (Duramite) is shown in the table. Thecomposition of the exemplary opacifying clusters is provided in thetable. CaCo₃ as used in the opacifying clusters is Omyacarb UF. Opaquepolymer commercially available from Dow is used in each sample. Thebalance of the composition of each sample is latex binder. The paintused comprises about 38% binder, 10% water, 13% large size extender (orequivalent opacifying cluster amounting to the 6.2 gallons provided inTable 2 below), 20% pigment slurry, and the balance being otheradditives.

TABLE 2 Properties of Various Extenders and/or Opacifying clustersPounds of Sample Composition Needed To Thickness of (Percentage Provide6.2 Applied CaCo3/Opaque Gallons of Coating Y-Value Y-Vahte ContrastSample Polymer/TiO₂) Extender (mils) (white) (black) Ratio S/Mil GlossSheen Duramite 100/0/0 140 2.5 0.9079 0.8548 0.942 1.86 10.8 11.5Example 6 42.5/42.5/5 89 2.5 0.9239 0.8881 0.961 2.43 7 7.3 Example 737.5/37.5/5 79 2.5 0.9204 0.8844 0.961 2.41 7.3 8.6 Example 8 45/45/0 832.5 0.9147 0.8754 0.957 2.18 7.9 8.6 Example 9 30/60/0 73 2.5 0.91820.8797 0.958 2.27 7.4 6.2 Example 10 0/90/0 51 2.5 0.9256 0.8901 0.9622.49 10.6 11.8 Example 11 43.75/43.75/2.5 85 2.5 0.9221 0.8854 0.9602.33 9.8 11.3 Example 12 20.1/58.4/2.5 75 2.5 0.9229 0.8879 0.962 2.4710.6 12.2 Example 13 0/85/5 57 2.5 0.9280 0.8942 0.964 2.59 11 14Example 14 42.5/42.5/5 90 2.5 0.9209 0.8841 0.960 2.43 10 14 Example 1530/60/0 51 2.5 0.9190 0.8775 0.955 2.25 8.6 9 Example 16 85/0/5 111 2.50.9184 0.8759 0.954 2.25 32 63 Example 17 80/0/5 118 2.5 0.9182 0.87480.953 2.19 13 17

Example 18

A comparison of opacifying clusters of the present disclosure toconventional opaque polymers (Ropaque) and conventional large sizeextenders (Duramite) in latex paint compositions was conducted. FIGS. 7and 8 illustrate opacity in terms of contrast ratio and sheen relativeto increasing PVC of the latex paint compositions. FIG. 7 illustratesthe ability of conventional opaque polymer and opacifying clustersherein to maintain or increase opacity with increasing PVC whileincreasing the amount of large size extenders leads to a dramaticdecrease in opacity. The drop in opacity with increasing volume of largesize extenders may be due to the large windows that such extenders formin the paint. FIG. 8 illustrates the unique ability of the opacifyingclusters herein to also function similar to large size extenders todecrease sheen. Conventional opaque polymers, as also shown in FIG. 8,are not able to decrease sheen like the opacifying clusters of thepresent disclosure and prior large size extenders. The composition ofthe opacifying clusters used for FIGS. 7 and 8 includes 2.5% TiO₂, 58.3%opaque polymer, 29.2% calcium carbonate, and 10% binder.

Example 19

The opacifying clusters herein also achieve the increased opacity withdesired burnish levels at the same time. Such burnish levels can also beachieved with decreasing or removing completely the levels of commonlyused durability increasing particles, such as polyvinyl chlorideparticles (PVC particles, Geon 215, PolyOne Corporation, about 22microns average size) to provide improved burnish.

For this example, spray dried opacifying clusters (SD clusters) wereprepared with about 29 volume percent small size extender (calciumcarbonate), 58.4 volume percent opaque polymer (Ropaque 96), about 2.5volume percent titanium dioxide, and 10 volume percent latex wereprepared according to the present disclosure. The SD clusters for thisExample had an average particle size of about 22 microns, which issimilar to the Geon particles. The clusters were added to a latex paintcomposition. The latex paint composition also included large sizeextenders (Minspar 4, the Quartz Corporation, about 7 microns averagesize), and opaque polymer (Ropaque 96). Tables 3 to 6 provide thecomposition of evaluated latex paints, opacity values, and burnishtesting of the exemplary clusters as compared to control paints usingthe Geon polyvinyl chloride particles instead.

TABLE 3 Latex Paint Compositions SD Clusters Opaque TiO2 ID SampleExtender Geon (22 microns) Polymer (slurry)* TiO2 (dry) NVV A Control 9050 0 85 300 0 41.1 B 18 90 0 51.5 85 300 0 41.1 C 19 90 0 71.4 85 225 041.1 D Control 30 55 0 0 0 45 33.3 E 20 30 0 56.6 0 0 45 33.3 F Control60 19 0 89.7 280 0 38.8 G 21 60 0 19.6 89.7 280 0 38.8 H Control 35.5 200 0 0 50 32.7 I 22 35.5 0 20.6 0 0 50 32.6 *75% slurry (amount of TiO2may he calculated by multiplying the listed amount by 0.75.)

TABLE 4 Opacity y- Opacity Factor value Y value 60 85 (Opacity/Dry IDSample PVC (white) (black) C/R s/mil gloss sheen TiO₂) A Control 38.80.919 0.874 0.952 2.11 5 3.6  1:106 B 18 49.3 (38.8) 0.925 0.893 0.9652.56 4.6 3.8 1:87 C 19 49.3 (38.8) 0.915 0.88 0.961 2.51 4.1 2.6 1:66 DControl 9  0.868 0.648 0.746 0.49 6.7 2.9 1:91 E 20 23.1 (9.0)  0.8710.701 0.805 0.72 5.6 2.9 1:62 F Control 37.2 0.923 0.888 0.962 2.56 10.513.9 1:82 G 21 4.17 (37.2) 0.928 0.899 0.969 2.64 9.1 11.6 1:79 HControl 10.6 10.866 0.682 0.788 0.63 14 13.4 1:79 I 22 15.9 (10.6) 0.8690.7005 0.812 0.75 12.7 12.1 1:66

TABLE 5 Burnish at 60 gloss % Increase % increase 60 gloss 60 gloss 60gloss (5 cycles) (25 cycles) Sample (initial) (5 cycles) (25 cycles)from Initial from Initial Control 5.3 5.7 5.9 8% 11% 18 5 5.4 5.7 8% 14%19 4.2 4.4 4.6 5% 10% Control — — — — — 20 — — — — — Control 10.6 12.212.2 15%  15% 21 9.2 10.6 10.8 15%  17% Control — — — — — 22 — — — — —

TABLE 6 Burnish at 85 Sheen 85 sheen % Increase % increase 85 Sheen 85Sheen (25 (5 cycles) (25 cycles) Sample (initial) (5 cycles) cycles)from Initial from Initial Control 3.7 4.4 5.1 19% 38% 18 3.8 4.8 5.1 26%34% 19 2.7 3.5 4.1 30% 52% Control — — — — — 20 — — — — — Control 13.5 14.7  15.1   9% 12% 21 11.5  12.9  13.3  12% 16% Control — — — — — 22 —— — — —

As shown, sample 18 achieves a better opacity in terms of contrast ratio(C/R) than its control (line above it) with the same paint compositionbut without the clusters and using Geon instead. Sample 19, whichreduces the level of TiO2 as compared to the control and sample 18,still achieves a better opacity than its control. Similar opacityresults are shown relative to controls for samples 20, 21, and 22. Allinvective samples achieved the desired opacity while maintainingacceptable burnish levels without the poly vinyl chloride durabilityparticles. Sample IDs A to E are matte finish and F to I are satinfinish.

Example 20

Another example comparing opacifying clusters of the present disclosureto latex paint compositions including or free of polyvinyl chlorideparticles similar to Example 19 was performed. For this Example, theopacifying clusters were of the same composition of Example 19, but hadan average particle size of about 17 microns. Tables 7 to 10 provide theresults.

TABLE 7 Latex Paint Compositions SD Clusters Ex- (17 Opaque TiO2 TiO2Sample tender Geon microns) Polymer (slurry)* (dry) NVV Control 90 50 085 300 0 41.1 23 90 0 51.5 85 300 0 41.1 24 125 0 51.5 85 225 0 41.1 25125 0 66.3 63.7 225 0 41.1 26 125 0 81.1 42.5 225 0 41.1 27 125 0 95.821.2 225 0 41.1 Control 60 19 0 89.7 280 0 38.8 28 60 0 19.6 89.7 280 038.8 *75% slurry (amount of TiO2 may be calculated by multiplying thelisted amount by 0.75.)

TABLE 8 Opacity y-value Y value 85 Sample PVC (white) (black) C/R s/mil60 gloss sheen Control 38.8 0.919 0.877 0.954 — 5 4 23 49.3 (38.8) 0.9270.893 0.964 — 5 5 24 49.2 (38.8) 0.92 0.877 0.953 — 4.9 4.9 25 49.2(38.8) 0.92 0.879 0.955 — 4.3 3.8 26 49.2 (38.8) 0.92 0.877 0.953 — 3.73.1 27 49.2 (38.8) 0.922 0.878 0.953 — 3.4 2.6 Control 37.2 0.924 0.8870.96 — 11 16 28 4.17 (37.2) 0.926 0.893 0.964 — 10 14

TABLE 9 Burnish at 60 Gloss % Increase % increase 60 gloss 60 gloss 60gloss (5 cycles) (25 cycles) Sample (initial) (5 cycles) (25 cycles)from Initial from Initial Control 4.9 5.4 5.6 10%  14% 23 4.8 5.3 5.610%  17% Control 5.2 5.6 5.9 8% 13 5 24 4.6 4.9 5 7%  9% 25 4.1 4.2 4.32%  5% 26 3.4 3.6 3.7 6%  9% 27 3.2 3.2 3.3 0%  3% Control 9.7 11.3 11.716%  21% 28 8.9 10.2 10.4 15%  17%

TABLE 10 Burnish at 85 Sheen 85 Sheen % Increase % increase 85 Sheen 85sheen (25 (5 cycles) (25 cycles) Sample (initial) (5 cycles) cycles)from Initial from Initial Control 43.5 4.5 4.9 29% 40% 23 4.6 6.1 6.833% 48% Control 3.6 4.3 4.5 19% 25% 24 4.3 5.2 6 21% 40% 25 3.4 4.6 5.135% 50% 26 2.7 3.8 5.2 41% 93% 27 2.4 4.1 5.3 71% 121%  Control 13 14.414.7 11% 13% 28 12 33.9 14.2 16% 18%

For both Examples 19 and 20, Y-value (white) is measured by ASTME1331-15; Y-value (black) is measured by ASTM E1331-15, contrast ratio(C/R) is measured by ASTM D2805; 60 gloss is measured by ASTM D523-14;85 Sheen is measured by ASTM D523-14 and Burnish is measured by ASTMD6736-08. In all examples and throughout this disclosure, unlessotherwise specified, all measurements herein are made at about 23±1° C.and about 50% relative humidity.

All publications, patent applications, and issued patents mentionedherein are hereby incorporated in their entirety by reference. Citationof any reference is not an admission regarding any determination as toits availability as prior art to the claimed disclosure.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, such as dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

While particular embodiments of the present disclosure have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the disclosure. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this disclosure.

A latex paint composition comprising:

solvent, at least one first polymeric binder, optional pigmentparticles, and a plurality of discrete opacifying cluster particles;

each discrete opacifying cluster particle includes a second polymericlatex binder coalescing cluster components into a generally homogeneousparticle wherein the second polymeric latex binder is the same as ordifferent from the at least one first polymeric binder;

the cluster components include discrete polymeric particles eachdefining a closed void volume therein, a plurality of optional inorganicpigment particles, and a plurality of extender pigment particles; and

a porosity of the polymeric latex binder defining a binder void volume.

The latex paint composition according to Claim 13, wherein a pigmentvolume concentration of the discrete opacifying cluster particles in thelatex paint composition is below the critical pigment volumeconcentration.

The latex paint composition of Claim 13, wherein each opacifying clusterparticle comprises a total void volume including a total closed voidvolume of all the discrete polymeric particles closed void volumes andthe binder void volume of the second polymeric latex binder.

The latex paint composition of Claim 15, wherein the total void volumeis from about 1% to about 35% by volume of the opacifying cluster.

The latex paint composition of Claim 13, wherein an average closed voidvolume of each discrete polymeric particle is about 0.4 microns to about0.7 microns in size.

The latex paint composition according to Claim 13, wherein the optionalpigment particles includes one of inorganic pigment particles,additional discrete polymeric particles each defining a closed voidvolume therein not coalesced within the opacifying cluster particles,extender pigment particles not coalesced within the opacifying clusterparticles, and mixtures thereof.

The latex paint composition according to Claim 18, wherein the latexpaint composition, when dried, includes about 50 to about 85 volumepercent of the first polymeric binder, about 0 to about 45 volumepercent extender pigment particles not coalesced within the opacifyingclusters particles, about 0 to about 20 volume percent discretepolymeric particles each defining a closed void volume therein notcoalesced within the opacifying cluster particles, about 0 to about 20volume percent inorganic pigment particles, and about 5 to about 50volume percent opacifying cluster particles.

The latex paint composition according to Claim 13, wherein theopacifying cluster particles have an outer surface defined at least by aportion of the second polymeric latex binder and wherein the outersurface has a surface porosity.

The latex paint composition according to Claim 20, wherein the surfaceporosity is formed by interstices each averaging in size from about0.050 microns to about 0.150 microns.

The latex paint composition according to Claim 13, wherein a glasstransition temperature of the discrete polymeric particles in theopacifying cluster particles is greater than a glass transitiontemperature of the second polymeric latex binder in the opacifyingcluster particles.

The latex paint composition of Claim 13, wherein each opacifying clusterparticle has an average particle size from about 5 microns to about 44microns.

The latex paint composition of Claim 13, wherein each opacifying clusterparticle includes from about 1% to about 30% by volume of the secondpolymeric latex binder, from about 10 to about 70 percent by volume ofthe discrete polymeric particles, from about 0 to about 6 percent byvolume of the inorganic pigment particles; and the balance being theextender pigment particles.

The latex paint composition of Claim 13, wherein the pigment volumeconcentration in the opacifying cluster is greater than or equal to acritical pigment volume concentration.

A latex paint composition exhibiting improved contrast ratio andopacity, the latex paint composition comprising.

solvent, a polymeric latex binder, pigment particles and a plurality ofspray dried opacifying cluster particles;

Each spray dried opacifying cluster particle including discretepolymeric particles each defining a closed void volume therein coalescedinto a generally homogeneous particle, optional polymeric binder,optional inorganic pigment particles, and optional pigment extenderparticles; and:

Wherein the latex paint composition, when dried as a paint film,exhibits about 10 to about 35 percentage increase in opacity as comparedto a latex paint composition with the same level of the pigmentparticles but not including the spray dried opacifying clusterparticles.

The latex paint composition of Claim 26, further exhibiting about 0.01to about 0.02 unit increase in contrast ratio as compared to a latexpaint composition with the same level of the pigment particles but notincluding the spray dried opacifying cluster particles.

The latex paint composition of Claim 26, wherein the improvement inopacity is exhibited over latex paint compositions with a gloss valuefrom about 0 to about 30 and a sheen value from about 0 to about 30.

The latex paint composition of Claim 26, wherein a dried latex paintcomposition exhibits less than about 20 percent increase in gloss andless than about 50 increase in sheen upon 25 scrub cycles per theprocedures of ASTM D6736-01.

The latex paint composition of Claim 29, wherein the latex paintcomposition includes less than about 10 weight percent of poly vinylchloride particles.

The latex paint composition of Claim 26, further comprising an opacityfactor of about 1:60 to about 1:90 in terms of a ratio of opacity to drypigment loading.

The latex paint composition of Claim 26, wherein the spray driedopacifying cluster particle has a total void volume including a totalclosed void volume of all the discrete polymeric particle closed voidvolumes and the binder void volume of the polymeric latex binder.

The latex paint composition of Claim 26, wherein the total void volumeis from about 1 percent to about 35 percent by volume of the spray driedopacifying cluster particle.

The latex paint composition of Claim 26, wherein an average closed voidvolume of each discrete polymeric particle is about 0.4 microns to about0.7 microns in size.

The latex paint composition of Claim 26, wherein an average particlesize of the spray dried opacifying cluster particle is from about 5microns to about 44 microns.

The latex paint composition of Claim 26, wherein the spray driedopacifying cluster particle has an outer surface defined at least by aportion of the polymeric latex binder and wherein the outer surface hasa surface porosity.

The latex paint composition of Claim 26, wherein the surface porosity isformed by one or more interstices each from about 0.050 μm to about0.150 μm in size.

The latex paint composition of Claim 26, wherein a glass transitiontemperature of the discrete polymeric particles is greater than a glasstransition temperature of the polymeric latex binder.

The latex paint composition of Claim 26, wherein the opacifying clusterincludes from about 1 percent to about 30 percent by volume of thepolymeric latex binder, from about 10 percent to about 70 percent byvolume of the discrete polymeric particles, from about 0 percent toabout 6 percent by volume of the inorganic pigment particles; and thebalance being the pigment extender particles.

The latex paint composition of Claim 26, wherein the pigment volumeconcentration in the spray dried opacifying cluster is greater than orequal to the critical pigment volume concentration.

The latex paint composition of Claim 26, wherein the optional extenderpigment particles are about 0.1 to about 1 microns in size and selectedfrom calcium carbonate, clay, silica, talc, and combinations thereof.

The latex paint composition of claim 26, further comprising an opacityfactor of about 1:60 to about 1:90 in terms of a ratio of opacity to drypigment loading.

A latex paint composition exhibiting improved contrast ratio and opacityover a range of gloss values, the latex paint composition comprising

Solvent, a polymeric latex binder, and pigment particles;

Wherein the latex paint composition, when dried as a paint film,exhibits about 10 to about 35 percentage increase in opacity as comparedto a latex paint composition with the same level of the pigmentparticles but not including the spray dried opacifying clusterparticles; and

Wherein the improvement in opacity is exhibited with latex paintcompositions having a gloss value from about 0 to about 30 and a sheenvalue from about 0 to about 30.

The latex paint composition of claim 43, further comprising a pluralityof spray dried opacifying cluster particles, wherein each spray driedopacifying cluster particle including discrete polymeric particles eachdefining a closed void volume therein coalesced into a generallyhomogeneous particle, optional polymeric binder, optional inorganicpigment particles, and optional pigment extender particles.

A particulate cluster for use in a coating composition, the particulatecluster comprises: (a) a first component having a first refractiveindex; (b) a second component having a second refractive index; whereinthe first component and the second component are connected by acoalesced latex binder material.

The particulate cluster of claim 45, wherein the first refractive indexof the first component is from about 1 to about 1.5 and the secondrefractive index of the second component is from about 1.5 to about 3.

The particulate cluster of claim 45, wherein the difference inrefractive index between the first component and the second component isabout 0.5 to about 2.0.

We claim:
 1. An opacifying cluster particle suitable for latex paintcompositions to provide increased opacity, the opacifying clusterparticle comprising: a polymeric latex binder coalescing clustercomponents into a generally homogeneous particle; the cluster componentsinclude discrete polymeric particles each defining a closed void volumetherein, a plurality of optional inorganic pigment particles, and aplurality of extender pigment particles; and a porosity of the polymericlatex binder defining a binder void volume.
 2. The opacifying clusterparticle of claim 1, wherein the opacifying cluster particle has a totalvoid volume including a total closed void volume of all the discretepolymeric particle closed void volumes and the binder void volume of thepolymeric latex binder.
 3. The opacifying cluster particle of claim 2,wherein the total void volume is from about 1 percent to about 35percent by volume of the opacifying cluster particle.
 4. The opacifyingcluster particle of claim 1, wherein an average closed void volume ofeach discrete polymeric particle is about 0.4 microns to about 0.7microns in size.
 5. The opacifying cluster particle of claim 1, whereinan average particle size of the opacifying cluster particle is fromabout 5 microns to about 44 microns.
 6. The opacifying cluster particleof claim 1, wherein the opacifying cluster particle has an outer surfacedefined at least by a portion of the polymeric latex binder and whereinthe outer surface has a surface porosity.
 7. The opacifying clusterparticle of claim 6, wherein the surface porosity is formed by one ormore interstices each from about 0.050 μm to about 0.150 μm in size. 8.The opacifying cluster particle of claim 1, wherein a glass transitiontemperature of the discrete polymeric particles is greater than a glasstransition temperature of the polymeric latex binder.
 9. The opacifyingcluster particle of claim 1, further comprising from about 1 percent toabout 30 percent by volume of the polymeric latex binder, from about 10percent to about 70 percent by volume of the discrete polymericparticles, from about 0 percent to about 6 percent by volume of theinorganic pigment particles; and the balance being the extender pigmentparticles.
 10. The opacifying cluster particle of claim 9, wherein thepigment volume concentration in the opacifying cluster particle isgreater than or equal to the critical pigment volume concentration. 11.The opacifying cluster particle of claim 1, wherein the extender pigmentparticles are about 0.1 to about 1 microns in size and selected fromcalcium carbonate, clay, silica, talc, and mixtures thereof.
 12. Theopacifying cluster particle of claim 1, wherein the inorganic pigmentparticles are about 0.1 to about 1.0 microns in size and selected fromtitanium dioxide, zinc oxide, and mixtures thereof.